CN102329223B - Method for preparing adipic acid through one-step oxidation of cyclohexane and catalyst used in method - Google Patents
Method for preparing adipic acid through one-step oxidation of cyclohexane and catalyst used in method Download PDFInfo
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Abstract
The invention discloses a method for preparing adipic acid through one-step oxidation of cyclohexane. The method comprises the following steps of: a, mixing the cyclohexane which is taken as a reactant and a phase transfer catalyst, fully stirring, adding an oxidant, and reacting for 4 to 12h at the temperature of between 140 and 180DEG C and under the pressure of between 0.5 and 2.5MPa to obtain a reaction product mixture, wherein the general formula of the phase transfer catalyst is QxPy[AB6O24]; and the structural formula of the phase transfer catalyst is shown in the specification, wherein x is more than or equal to 1 and is less than or equal to 10 and x+y is less than or equal to 10; and b, cooling the reaction product mixture obtained in step a to room temperature, filtering, washing by using a cleaning solution to obtain a solid, and drying the obtained solid to obtain the adipic acid. The invention also provides a catalyst used in preparation of the adipic acid by oxidizing the cyclohexane. The catalyst has strong catalytic activity and selectivity.
Description
Technical field
The present invention relates to method and the method catalyzer used that a kind of hexanaphthene oxidation step prepares hexanodioic acid.
Background technology
Hexanodioic acid (adipic acid) claims again adipic acid, is a kind of important organic dibasic acid, can generate polyester polyol with polyol reaction, and then produces polyurethane products; Hexanodioic acid is the important source material of nylon 66 fiber and nylon resin; Hexanodioic acid also can be applicable to lubricant, softening agent and pharmaceutical industries.Hexanodioic acid is used for nylon 66 fields and surpasses 70% in the world, and the field that China's hexanodioic acid is used for urethane reaches 78%, 2009 year global hexanodioic acid production capacity and reaches 3,300,000 tons.Present industrial synthesizing adipic acid is mainly nitric acid oxidation method.The method is due to the concentrated nitric acid that uses strong oxidizing property, and equipment corrosion is serious, and the N that produces
2O is considered to one of reason that causes Global warming and ozone reduction, causes great pollution to environment; Add that energy consumption is high, perplexing the development of adipic acid technology always.Along with the rise of Green Chemistry, seeking novel process efficient, environmental protection has become the focus in synthesizing adipic acid field in recent years.Oxygen has obvious advantage as oxygenant: the source is abundant, and corrodibility is little, does not produce environmental pollutant.
The production method of hexanodioic acid has four kinds of phynol method, hexanaphthene method, the cyclohexene method and butadiene processs etc. in the world at present.Before the fifties, hexanodioic acid production is mainly take phenol as raw material, and producing hexanodioic acid with phynol method is a kind of more classic method, and this method advantage is that product purity is high, and production technology is ripe.But the phenol resource-constrained, and expensive, product cost is high, and is substantially superseded at present.The hexanaphthene method is mainly adopted in modern industry production, has also developed the cyclohexene method and butadiene process.Hexanaphthene method (claiming again KA oil (mixture of hexalin and pimelinketone) method), this method is the main method of synthesizing adipic acid, its output accounts for 93% of ultimate production, generally first to synthesize KA oil, the raw material of synthetic KA oil is generally used hexanaphthene (88%), the mixture of benzene (5%) and phenol (7%), then oxidation KA oil synthesizing adipic acid.The advantage of this method is: this technique is the most traditional hexanodioic acid synthesis technique, occupies an leading position in hexanodioic acid production, and productive rate is generally in 76% left and right, and by product is mainly succinic acid and pentanedioic acid, and is easily separated, and product is purer.Its weak point: this technique is at synthetic KA oil, and per pass conversion is lower, especially uses hexanaphthene, transformation efficiency is generally 5% ~ 12%, and oxygenant used is nitric acid when being oxidizing to hexanodioic acid by KA, can emit a large amount of oxynitride, serious environment pollution, High Temperature High Pressure in addition, energy consumption is high.
Chinese patent ZL 03118249.6 and CN 101337879 B disclose the method for catalysis of metalloporphyrin oxygen, oxidizing ethyle alkyl or hexanaphthene, pimelinketone, hexalin mixed solution synthesizing adipic acid, the method is homogeneous reaction, catalytic efficiency is high, but metalloporphyrin type catalyzer is expensive, the preparation method is complicated, long reaction time, reaction by-product is many.In addition, Chinese patent CN101337878 B and CN1020405 A disclose and have prepared the method for hexanodioic acid take carbon nanotube as catalyst rings hexane oxidation step, the method is heterogeneous reaction, catalyzer can be repeatedly used, but need a large amount of solvents and initiator in reaction process, increased cost.
Summary of the invention
In order to solve above the deficiencies in the prior art, the object of the present invention is to provide a kind ofly take heteropolyacid as catalyzer, take oxygen or air as oxygenant, the hexanaphthene oxidation step prepares the method for hexanodioic acid.The method is take a kind of heteropolyacid as catalyzer, take molecular oxygen or air as oxygenant, not with an organic solvent as reaction medium, avoids nitric acid to make oxygenant to the pollution of environment.140 ~ 180 ℃ of temperature of reaction, reaction pressure (oxygen) 0.5 ~ 2.5 MPa, in 4 ~ 12 hours reaction times, the per pass conversion of hexanaphthene can reach 20 ~ 50%, and the one way molar yield of hexanodioic acid can reach 5 ~ 10%.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of hexanaphthene oxidation step prepares the method for hexanodioic acid, comprises following processing step:
Step a, hexanaphthene is mixed with phase-transfer catalyst, fully stir, after catalyst dissolution, pass into the air or oxygen oxygenant, 140 ~ 180 ℃ of temperature, under the condition of pressure 0.5 ~ 2.5 MPa, reaction 4 ~ 12h obtains mixture of reaction products, and described oxygenant is oxygen or air, described phase-transfer catalyst is heteropolyacid, and its general formula is Q
xP
y[AB
6O
24], its structural formula is:
Wherein, 1≤x≤10 1≤y≤10-x;
A refers to the central atom of heteropoly compound, and it comprises and a kind of in iodine (I), iron (Fe), molybdenum (Mo), aluminium (Al), cobalt (Co), copper (Cu), nickel (Ni), zinc (Zn) etc. is preferably iodine (I), molybdenum (Mo) or cobalt (Co);
B refers to the heteroatoms of heteropoly compound, and it comprises molybdenum (Mo) or tungsten (W);
P refers to Na
+, NH
4 +Or H
+Deng positively charged ion.
Step b, after the mixture of reaction products that step a obtains is cooled to room temperature (20 ℃ of left and right), filtering and using fresh cyclohexane give is that washings washs and obtains solid, the gained solid is carried out drying, namely get hexanodioic acid (containing a small amount of succinic acid and pentanedioic acid), comprise unreacted hexanaphthene and partial oxidation products KA oil in filtrate after filtration, adding unreacted fresh cyclohexane give in filtrate is reactant, add again catalyzer to continue reaction under the processing condition of step a, until complete reaction.
Further, described Q represents that molecular formula is (C
nH
2n+1)
4N
+Quaternary ammonium salt cationic, wherein, the span of n is 1≤n≤18.The carbon chain lengths that has a group at least in preferred quaternary ammonium salt cationic is more than or equal to 8 carbon atoms, and preferred carbonatoms is quaternary ammonium salt cationic or its combination of 12,16,18 alkyl, preferably consists of (C
18H
37)
3N
+CH
3Quaternary ammonium salt, that is:
Described quaternary ammonium salt cationic is (C
8H
17)
4N
+,
(C
12H
25)
4?N
+、
(C
18H
37)?N
+(CH
3)
3、
(p~C
5H
5?N
+C
16H
33)、
(C
18H
37)
2N
+(CH
3)
2In one or more,
Be preferably (C
12H
25)
4N
+,
(C
18H
37)?N
+(CH
3)
3、
(p~C
5H
5N
+C
16H
33)、
(C
18H
37) N
+(CH
3)
3In one or more,
(C preferably
18H
37) N
+(CH
3)
3,
(p~C
5H
5N
+C
16H
33)、
(C
18H
37)
2N
+(CH
3)
2In one or more.
Another object of the present invention is to provide a kind of catalyzer for preparing the hexanodioic acid method for oxidizing ethyle alkyl, it is characterized in that: said catalyst molecule formula is Q
xP
y[AB
6O
24],, its structural formula is:
Wherein, Q represents that the season molecular formula is for (C
nH
2n+1)
4N
+The ammonium salt positively charged ion, 1≤n≤18;
P is Na
+, NH
4 +Or H
+Deng positively charged ion;
A represents a kind of in iodine, iron, molybdenum, aluminium, cobalt, copper, nickel, zinc;
B is molybdenum or tungsten;
1≤x≤10，1≤y≤10-x。
The invention has the beneficial effects as follows: its technological process of method that hexanaphthene oxidation step of the present invention prepares hexanodioic acid oxidizing ethyle alkyl is effectively produced hexanodioic acid, catalyzer used has extremely strong catalytic activity and selectivity, and be that reactant is again directly as solvent with hexanaphthene, with air or oxygen as oxygenant, there is no other by products, as N
2O etc. avoid the pollution of using nitric acid as oxygenant, environment to be produced.
Specifically, compared with prior art, the production method that oxidizing ethyle alkyl of the present invention prepares hexanodioic acid has the following advantages:
1, take oxygen or air as oxygenant, hexanaphthene is carried out oxidation, produce hexanodioic acid, with low cost, be non-harmful Green Chemistry, be the target that scientific circles and industry member are pursued always.
2, catalyzer used has extremely strong catalytic activity and selectivity, and the per pass conversion of hexanaphthene can reach 20 ~ 50%, and the one way molar yield of hexanodioic acid can reach 10 ~ 30%.
Embodiment
Mode by the following examples further illustrates the present invention, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
The preparation of catalyzer: with Na
5IMo
6O
241.23g (1 mmol) is dissolved in 20 ml deionized waters, separately getting octadecyl trimethyl ammonium chloride 2.09 g (6 mmol) is dissolved in 10 ml dehydrated alcohols, after heat makes the octadecyl trimethyl ammonium chloride CL a little, splash into slowly in the aqueous solution of iodine Sodium orthomolybdate, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [C
18H
37N (CH
3)
3]
5[IMo
6O
24], structural formula is
Heteropolyacid catalyst.
The hexanaphthene oxidation step prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [C with above-mentioned molecular formula
18H
37N (CH
3)
3]
5[IMo
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 10ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 160 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 2.0MPa, reacted 6 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 5.2 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 20%, the molar yield 7.7% of hexanodioic acid.
The secondary oxidation hexanaphthene prepares hexanodioic acid: be reactant (volume of reactant is 50 mL) with adding fresh cyclohexane give in the filtrate that obtains after filtering after once oxidation, replenishing appropriate catalyzer makes the content of catalyzer remain on 10ppm, repeat again the oxidising process that above-mentioned hexanaphthene oxidation step prepares hexanodioic acid, get at last approximately 5.4 grams of solid, be hexanodioic acid.By liquid-phase chromatographic analysis, molar yield 8.0 % of hexanodioic acid.
Three times oxidizing ethyle alkyl prepares hexanodioic acid: be reactant (volume of reactant is 50 mL) with adding fresh cyclohexane give in the filtrate that obtains after filtering after secondary oxidation, replenishing appropriate catalyzer makes the content of catalyzer remain on 10ppm, repeat again the oxidising process that above-mentioned hexanaphthene oxidation step prepares hexanodioic acid, get at last approximately 6.6 grams of solid, be hexanodioic acid.By liquid-phase chromatographic analysis, molar yield 9.8 % of hexanodioic acid.
Four times oxidizing ethyle alkyl prepares hexanodioic acid: be reactant (volume of reactant is 50 mL) with obtaining adding in filtrate fresh cyclohexane give after filtering after once oxidation, replenishing appropriate catalyzer makes the content of catalyzer remain on 10ppm, repeat again the oxidising process that above-mentioned hexanaphthene oxidation step prepares hexanodioic acid, get at last approximately 5.0 grams of solid, be hexanodioic acid.By liquid-phase chromatographic analysis, molar yield 7.4 % of hexanodioic acid.
Embodiment 2
The preparation of catalyzer: with Na
3H
6CoW
6O
241.78g (1 mmol) is dissolved in 20 ml deionized waters, separately getting distearyl dimethyl ammonium chloride 3.52 g (6 mmol) is dissolved in 10 ml dehydrated alcohols, after heat makes the octadecyl trimethyl ammonium chloride CL a little, splash into slowly in the aqueous solution of cobaltous tungstate, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(C
18H
37)
2N (CH
3)
2]
6Na
3[CoW
6O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(C with above-mentioned molecular formula
18H
37)
2N (CH
3)
2]
6Na
3[CoW
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 1 ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 147 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 1.5 MPa, reacted 9 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 4.2 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 16%, molar yield 6.2 % of hexanodioic acid.
Be reactant (volume of reactant is 50 mL) with adding fresh cyclohexane give in the filtrate that obtains after filtering, replenish appropriate catalyzer and make the content of catalyzer remain on 1 ppm, then repeat the process that above-mentioned oxidizing ethyle alkyl prepares hexanodioic acid.
Embodiment 3
The preparation of catalyzer: with Na
4H
6Ni Mo
6O
241.11 g (1 mmol) is dissolved in 20 ml deionized waters, separately getting cetylpyridinium chloride 2.04 g (6 mmol) is dissolved in 10 ml dehydrated alcohols, splash into slowly in the aqueous solution of nickel molybdic acid, while vigorous stirring 4h, the white precipitate that obtains filters, and washing is under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(p ~ C
5H
5N
+C
16H
33]
6Na
4[NiMo
6O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(p ~ C with above-mentioned molecular formula
5H
5N
+C
16H
33]
6Na
4[NiMo
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 5 ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 150 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 2.0MPa, reacted 9 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 5.7 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 24%, molar yield 8.5 % of hexanodioic acid.
Embodiment 4
The preparation of catalyzer: with (NH
4)
6Mo
7O
241.21g (1 mmol) is dissolved in 20 ml deionized waters, separately getting distearyl dimethyl ammonium chloride 3.52 g (6 mmol) is dissolved in 10 ml dehydrated alcohols, heat is dissolved distearyl dimethyl ammonium chloride fully a little, splash into slowly in the aqueous solution of ammonium molybdate, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(C
18H
37)
2N (CH
3)
2]
6[Mo
7O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(C with above-mentioned molecular formula
18H
37)
2N (CH
3)
2]
6[Mo
7O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 1 ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 180 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 1.0MPa, reacted 6 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 4.5 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 25 %, molar yield 6.7 % of hexanodioic acid.
Embodiment 5
The preparation of catalyzer: with Na
4H
6FeMo
6O
241.11 (1 mmol) is dissolved in 20 ml deionized waters, separately getting distearyl dimethyl ammonium chloride 1.76 g (3 mmol) is dissolved in 10 ml dehydrated alcohols, after heat is dissolved distearyl dimethyl ammonium chloride fully a little, splash into slowly in the aqueous solution of molybdic acid aluminium, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(C
18H
37)
2N (CH
3)
2]
6Na
4[Fe Mo
6O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(C with above-mentioned molecular formula
18H
37)
2N (CH
3)
2]
3H
3Na
4[Fe Mo
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 10ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 150 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 2.5MPa, reacted 9 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 4.9 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 16%, molar yield 7.3 % of hexanodioic acid.
Embodiment 6
The preparation of catalyzer: with Na
4H
6Zn Mo
6O
241.06g (1 mmol) is dissolved in 20 ml deionized waters, separately getting distearyl dimethyl ammonium chloride 0.58 g (1 mmol) is dissolved in 10 ml dehydrated alcohols, after heat is dissolved distearyl dimethyl ammonium chloride fully a little, splash into slowly in the aqueous solution of molybdic acid aluminium, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(C
18H
37)
2N (CH
3)
2]
6Na
4[Zn Mo
6O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(C with above-mentioned molecular formula
18H
37)
2N (CH
3)
2] H
5Na
4[Zn Mo
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 1 ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.2 MPa, be warming up to 140 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 0.5MPa, reacted 4 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 3.2 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 16%, the molar yield 4.8% of hexanodioic acid.
Embodiment 7
The preparation of catalyzer: with Na
4H
6Cu Mo
6O
241.12 g (1 mmol) is dissolved in 20 ml deionized waters, separately getting distearyl dimethyl ammonium chloride 3.52 g (6 mmol) is dissolved in 10 ml dehydrated alcohols, heat is dissolved distearyl dimethyl ammonium chloride fully a little, splash into slowly in the aqueous solution of molybdic acid aluminium, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(C
18H
37)
2N (CH
3)
2]
6Na
4[CuMo
6O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(C with above-mentioned molecular formula
18H
37)
2N (CH
3)
2]
6Na
4[Cu Mo
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 10ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 1.0 MPa, be warming up to 155 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 2.5MPa, reacted 12 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 4.0 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 28%, molar yield 6 % of hexanodioic acid.
Embodiment 8
The preparation of catalyzer: with Na
3H
6Al Mo
6O
241.06 g (1 mmol) is dissolved in 20 ml deionized waters, separately getting distearyl dimethyl ammonium chloride 3.52 g (6 mmol) is dissolved in 10 ml dehydrated alcohols, heat is dissolved distearyl dimethyl ammonium chloride fully a little, splash into slowly in the aqueous solution of molybdic acid aluminium, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [(C
18H
37)
2N (CH
3)
2]
6Na
3[Al Mo
6O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [(C with above-mentioned molecular formula
18H
37)
2N (CH
3)
2]
6Na
3[Al Mo
6O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 5 ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 150 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 2.0MPa, reacted 9 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 4.3 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 25 %, molar yield 6.4 % of hexanodioic acid.
Embodiment 9
The preparation of catalyzer: with (NH
4)
6Mo
7O
241.21g (1 mmol) is dissolved in 20 ml deionized waters, separately getting Dodecyl trimethyl ammonium chloride 1.39 g (4 mmol) is dissolved in 10 ml dehydrated alcohols, heat is dissolved Dodecyl trimethyl ammonium chloride fully a little, splash into slowly in the aqueous solution of ammonium molybdate, while vigorous stirring 4h, the white precipitate that obtains filters, washing, under vacuum condition, 60 ℃ of drying 24 h namely get molecular formula and are [C
12H
33N (CH
3)
3]
4(NH
4)
2[Mo
7O
24], structural formula is
Heteropolyacid catalyst.
Oxidizing ethyle alkyl prepares hexanodioic acid: hexanaphthene 50 ml are added in the 160ml autoclave, are [C with above-mentioned molecular formula
12H
33N (CH
3)
3]
4(NH
4)
2[Mo
7O
24] heteropolyacid catalyst be dissolved in hexanaphthene, magnetic agitation, the concentration of catalyzer is 1 ppm, then passing into oxygen to high pressure reacting kettle inner pressure is 0.5 MPa, be warming up to 147 ℃, continuing to pass into oxygen oxygen to the high pressure reactor presses and is stabilized to 1.0MPa, reacted 4 hours, stopped reaction obtains mixture of reaction products, the mixture of reaction products that obtains is down to room temperature, filtered liquid solid state reaction product mixtures obtains white solid, the dry white solid that obtains under 60 ℃ of vacuum conditions, get at last approximately 2.5 grams of solid, be hexanodioic acid.Transformation efficiency by gas-chromatography and liquid-phase chromatographic analysis proof hexanaphthene is 20 %, molar yield 3.7 % of hexanodioic acid.
The above is only preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a hexanaphthene oxidation step prepares the method for hexanodioic acid, it is characterized in that, comprises following processing step:
Step a, be that reactant mixes with phase-transfer catalyst with cyclohexane give, after fully stirring, add oxygenant, 140 ~ 180 ℃ of temperature, under the condition of pressure 0.5 ~ 2.5 MPa, reaction 4 ~ 12h obtains mixture of reaction products; Described phase-transfer catalyst is heteropolyacid, and its general formula is Q
xP
y[AB
6O
24], structural formula is:
Wherein, 1≤x≤10,1≤y≤10-x; Central atom A is iodine, iron, molybdenum, aluminium, cobalt, copper, nickel or zinc; Heteroatoms B is molybdenum or tungsten; Q represents that molecular formula is (C
nH
2n+1)
4N
+Quaternary ammonium salt cationic, 1≤n≤18; Described P represents positively charged ion Na
+, NH
4 +Or H
+
Step b, after the mixture of reaction products that step a obtains is cooled to room temperature, filter and obtain solid with after washings washing, the gained solid is carried out drying, namely get hexanodioic acid,
Wherein, in step a, described oxygenant is oxygen.
2. a kind of hexanaphthene oxidation step according to claim 1 prepares the method for hexanodioic acid, and it is characterized in that: described quaternary ammonium salt cationic is (C
8H
17)
4N
+, (C
12H
25)
4N
+, (C
18H
37) N
+(CH
3)
3, (C
18H
37)
2N
+(CH
3)
2In one or more.
3. a kind of hexanaphthene oxidation step according to claim 1 prepares the method for hexanodioic acid, it is characterized in that: in described step b, washings is hexanaphthene.
4. the described a kind of hexanaphthene oxidation step of according to claim 1 to 3 any one prepares the method for hexanodioic acid, it is characterized in that: the filtrate after filtering in described step b adds after fresh cyclohexane as the reactant process of repeating step a, step b again.
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Non-Patent Citations (4)
| Title |
|---|
| Aerobic Oxidation of Vicinal Diols Catalyzed by an Anderson-Type Polyoxometalate, [IMo6O24]5-;Alexander M. Khenkin et al.;《Adv. Synth. Catal.》;20021231;第344卷(第9期);第1017-1021页 * |
| Aerobic oxidative desulfurization of benzothiophene, dibenzothiophene and 4,6-dimethyldibenzothiophene using an Anderson-type catalyst [(C18H37)2N(CH3)2]5[IMo6O24];Hongying Lü et al.;《Green Chem.》;20101004;第12卷;第1954–1958页 * |
| Alexander M. Khenkin et al..Aerobic Oxidation of Vicinal Diols Catalyzed by an Anderson-Type Polyoxometalate, [IMo6O24]5-.《Adv. Synth. Catal.》.2002,第344卷(第9期),第1017-1021页. |
| Hongying Lü et al..Aerobic oxidative desulfurization of benzothiophene, dibenzothiophene and 4,6-dimethyldibenzothiophene using an Anderson-type catalyst [(C18H37)2N(CH3)2]5[IMo6O24].《Green Chem.》.2010,第12卷第1954–1958页. |
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